Process for manufacturing high to ultra high molecular weight polymers using novel bridged metallocene catalysts

ABSTRACT

The present invention relates to a process of manufacturing high, very high, and ultra high molecular weight polymers comprising predominantly ethylene monomers. Ethylene is reacted in the presence of a catalyst system to produce a polymer having a viscosimetrically-determined molecular weight of at least 0.7×10 6  g/mol. The catalyst system generally includes a bridged metallocene catalyst compound, optionally with a co-catalyst. The catalyst is characterized by a zirconium dichloride central functionality and a dimethyl silandiyl bridge between five-membered rings of indenyl groups. Both rings of the metallocene compound are substituted at the 2-position with respect to the dimethyl silandiyl bridge with a C 1 -C 20  carbonaceous group.

CLAIM FOR PRIORITY

This Non-Provisional patent application is a continuation-in-part ofU.S. patent application Ser. No. 11/592,538 entitled “Process forManufacturing Ultra High Molecular Weight Polymers Using Novel BridgedMetallocene Catalysts”, filed on Nov. 3, 2006, the priority of which isclaimed, and the disclosure of which is incorporated by reference. Thisapplication is based on German Patent Application No. DE 10 2005052654.3, filed Nov. 4, 2005, and also U.S. Provisional PatentApplication No. 60/735,438, filed in the German language on Nov. 10,2005, the priorities of which are hereby claimed. Both documents areincorporated into this application in their entireties by reference. AnEnglish language translation of the '438 United States ProvisionalApplication was filed on May 26, 2006, the entirety of which is alsoincorporated herein by reference.

TECHNICAL FIELD

The invention relates to a process of manufacturing high to ultra highmolecular weight polymers via the polymerization and co-polymerizationof olefins using catalysts and their catalyst systems.

BACKGROUND OF THE INVENTION

Ultra high molecular weight ethylene polymers refer to those having aviscosimetrically determined molecular weight of greater than 1×10⁶g/mol. Because of their extraordinary properties, such as higherabrasion resistance and low sliding friction, such polymers have amultitude of uses. Consequently, they are used in materials handling,bulk materials handling, as well as in medical applications such asjoint sockets in prosthetic joints.

High and very high molecular weight ethylene polymers refer to thosehaving a viscosimetrically determined molecular weight of greater thanthat of a conventional high-density polyethylene, for example, greaterthan about 400,000 g/mol, and less than that of an ultra high molecularweight polyethylene. Such polymers have good impact strength andabrasion resistance, although somewhat lower than that of ultra highmolecular weight ethylene polymers. They are melt processible and areused, for example, in food handling cutting boards and ortheses.

Because of these novel properties, the processing of high to ultra highmolecular weight polyethylene is highly complex. Ram-extrusion andcompression molding of powdered raw materials are processes used toproduce molded parts, whereby the molded parts manufactured often stillexhibit the characteristics of the raw powder. Films and fibers areproduced using solution or gel processes, which require large amounts ofsolvents. An objective is therefore to develop new high to ultra highmolecular weight polyethylenes, which have improved processability.

According to the present state of technology, ultra high molecularweight polyethylene is manufactured according to the low pressureprocess using heterogeneous Ziegler catalysts. Such catalysts are, forexample, described in the following patent documents: EP186995,DE3833445, EP575840 and U.S. Pat. No. 6,559,249.

Other known catalysts for olefin polymerization are single sitecatalysts. According to the present state of technology, ultra highmolecular weight polymers are manufactured using these catalysts only inexceptional cases and under economically unprofitable conditions.Consequently, heterogeneous constrained-geometry catalysts form ultrahigh molecular weight polyethylene only with moderate activity andincreased long chain branching, which can lead to reduced hardness andworse abrasion properties. With so-called phenoxy-imine catalysts,UHMWPE is obtained only at low activity at economically unprofitabletemperature levels. Examples of these as well as other metallocenes aredescribed in WO9719959, WO0155231, Adv. Synth. Catal 2002, 344, 477-493,EP0798306, as well as in EP0643078.

While some bridged metallocene catalysts are known, the catalysts havenot been taught in a heterogeneous polymerization process in such a wayas to achieve high to ultra high molecular weight in production ofethylene homopolymers and copolymers comprising predominantly ethylenemonomers. Examples of such catalysts are described in U.S. Pat. Nos.6,417,302; 7,005,398; 7,109,278; and 7,169,864.

Surprisingly, bridged single site catalysts with a suitable ligandstructure were found in connection with the present invention, whichwhen optionally used with aluminoxanes as co-catalysts, not onlypermitted the manufacture of ultra high molecular weight polyethyleneswith a viscosimetrically determined molecular weight of at least about0.7×10⁶ g/mol, but also produced products with improved processability.The reason for the improved processability, without being bound to atheory, has to do with the narrower molecular weight distribution Mw/Mnof 2 to 6 compared to polymers that were manufactured using Zieglercatalysts and have a molecular weight distribution Mw/Mn of 3 to 30.

SUMMARY OF THE INVENTION

According to one aspect of the present invention, there is provided anovel process for manufacturing high, very high, and ultra highmolecular weight polymers comprising predominantly ethylene monomers.The process comprises reacting ethylene, and optionally other olefinmonomers, in the presence of a catalyst system which includes bridgedmetallocene catalysts of the type having the following general formula:

whereby:

-   -   M¹ is a transition metal of the 4^(th) to 6^(th) group of the        periodic table, whose oxidation level does not equal zero, and        is preferably Ti, Zr, Hf, V, Mo, Cr and Nb;    -   R¹ is hydrogen or a C₁-C₂₀-carbonaceous group or a halogen atom;    -   R² is hydrogen or a C₁-C₂₀ carbonaceous group or a halogen atom;    -   R³ and R¹⁰ are each identical or different and are each a C₁-C₂₀        carbonaceous group;    -   R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, and R¹⁵ are each        identical or different and are each hydrogen or a halogen atom        or a C₁-C₂₀ carbonaceous group, whereby, optionally, two or more        consecutively form a cyclic system, and preferably at least one        includes a cyclic group; and    -   R⁹ is a bridge between the ligands, which is represented by one        of the following formulas:

whereby:

-   -   M² is either silicon, germanium or tin; and    -   R¹⁶ and R¹⁷ are each identical or different and equal to        hydrogen or a C₁-C₂₀ carbonaceous group or a halogen atom.

The catalyst system optionally includes a co-catalyst. The processproduces a polymer having a viscosimetrically-determined molecularweight of 0.7×10⁶ g/mol or greater.

The process according to the invention contradicts the prejudice thatthe economical manufacture of ultra high molecular weight polymers isimpossible using aluminoxanes as co-catalysts. Through the novel ligandstructure of the inventions, the catalyst is believed to be stericallyshielded enough against the primary mechanism for low molecular weightproducts to result, namely the chain transfer to aluminoxane, withouthowever losing its economically necessary activity to the monomers.Still further features and advantages of the invention are apparent fromthe following description and claims.

DETAILED DESCRIPTION OF THE INVENTION

The invention is described in detail below with reference to severalembodiments and numerous examples. Such discussion is for purposes ofillustration only. Modifications to particular examples within thespirit and scope of the present invention, set forth in the appendedclaims, will be readily apparent to one of skill in the art. Terminologyused herein is given its ordinary meaning consistent with the exemplarydefinitions set forth immediately below.

As used herein, the term “heterogenization”, and like terms, refers toactivation of a catalyst with a co-catalyst and deposition on a support.This is also referred to herein as production of a supported catalyst.

In the present invention, a C₁-C₂₀ carbonaceous group is understood tobe preferably the radicals:

-   -   C₁-C₂₀ alkyl, in particular methyl, ethyl, n-propyl, i-propyl,        n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl,        cyclopentyl, n-hexyl, cyclohexyl, n-octyl, or cyclooctyl;    -   C₂-C₂₀ alkenyl, in particular ethenyl, propenyl, butenyl,        pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, octenyl or        cyclooctenyl;    -   C₂-C₂₀ alkinyl, in particular ethynyl, propynyl, butynyl,        pentynyl, hexynyl or octynyl;    -   C₆-C₂₀ aryl, in particular benzylidene, o-methoxybenzylidene,        2,6-dimethylbenzylidene, phenyl, biphenyl, naphthyl,        anthracenyl, triphenylenyl, [1,1′,3′, 1″]-terphenyl-2′-yl,        binaphthyl, or phenanthrenyl;    -   C₁-C₂₀ fluoroalkyl, in particular trifluoromethyl,        pentafluoroethyl, 2,2,2-trifluoroethyl, 3-trifluoropropyl, or        2,2′-trifluoroisopropyl;    -   C₆-C₂₀ fluoroaryl, in particular pentafluorophenyl,        3,5-bistrifluoromethylphenyl, pentafluorobenzylidene,        3,5-bistrifluoromethylbenzylidene, tetrafluorophenyl, or        heptafluoronaphthyl;    -   C₁-C₂₀ alkoxy, in particular methoxy, ethoxy, n-propoxy,        i-propoxy, n-butoxy, i-butoxy, s-butoxy, or t-butoxy;    -   C₆-C₂₀ aryloxy, in particular phenoxy, naphthoxy, biphenyloxy,        anthracenyloxy, or phenanthrenyloxy;    -   C₇-C₂₀ arylalkyl, in particular o-tolyl, m-tolyl, p-tolyl,        2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-di-1-propylphenyl,        2,6-di-t-butylphenyl, o-t-butylphenyl, m-t-butylphenyl, or        p-t-butylphenyl;    -   C₇-C₂₀ alkylaryl, in particular benzyl, ethylphenyl,        propylphenyl, diphenylmethyl, triphenylmethyl, or methyl        naphthalene;    -   C₇-C₂₀ aryloxyalkyl, in particular o-methoxyphenyl,        m-methoxyphenyl, or p-methoxyphenyl;    -   C₁₂-C₂₀ aryloxyaryl, in particular p-phenoxyphenyl;    -   C₅-C₂₀ heteroaryl, in particular 2-pyridyl, 3-pyridyl,        4-pyridyl, chinolinyl, isochinolinyl, acridinyl,        benzochinolinyl, or benzoisochinolinyl;    -   C₄-C₂₀ heterocycloalkyl, in particular furyl, benzofuryl,        2-pyrrolidinyl, 2-indolyl, 3-indolyl, or 2,3-dihydroindolyl;    -   C₈-C₂₀ arylalkenyl, in particular o-vinylphenyl, m-vinylphenyl,        or p-vinylphenyl;    -   C₈-C₂₀ arylalkinyl, in particular o-ethynylphenyl,        m-ethynylphenyl, or p-ethynylphenyl;    -   C₁-C₂₀ heteroatomic group, in particular carbonyl, benzoyl,        oxybenzoyl, benzoyloxy, acetyl, acetoxy, or nitrile; whereby one        or more C₁-C₂₀ carbonaceous groups can form a cyclic system.

The object of the present invention is a process to manufacture high,very high, and ultra high molecular weight polymers using the compoundsof Formula I:

whereby:

-   -   M¹ is a transition metal of the 4^(th) to 6^(th) group of the        periodic table, whose oxidation level does not equal zero, and        is preferably Ti, Zr, Hf, V, Mo, Cr and Nb;    -   R¹ is hydrogen or a C₁-C₂₀-carbonaceous group or a halogen atom;    -   R² is hydrogen or a C₁-C₂₀ carbonaceous group or a halogen atom;    -   R³ and R¹⁰ are each identical or different and are each a C₁-C₂₀        carbonaceous group;    -   R⁴, R⁵, R⁶, R⁷, R⁸, R¹, R¹², R¹³, R¹⁴, and R¹⁵ are each        identical or different and are each hydrogen or a halogen atom        or a C₁-C₂₀ carbonaceous group, whereby, optionally, two or more        consecutively form a cyclic system, and preferably at least one        includes a cyclic group; and    -   R⁹ forms a bridge between the ligands, which can be shown by the        following formulas:

whereby:

-   -   M² is either silicon, germanium or tin; and    -   R¹⁶ and R¹⁷ are each identical or different and equal to        hydrogen or    -   a C₁-C₂₀ carbonaceous group or a halogen atom.

In a preferred embodiment of the invention, for Formula I:

-   -   M¹ shall be a transition metal of the 4^(th) group of the        periodic table, whose oxidation level does not equal zero, and        is preferably Ti, Zr or Hf;    -   R¹ shall be hydrogen, a C₁-C₂₀-carbonaceous group, or a halogen        atom;    -   R² shall be hydrogen, a C₁-C₂₀ carbonaceous group, or a halogen        atom;    -   R³ shall be a C₁-C₂₀ carbonaceous group, preferably one cyclized        in an α- or β-position or one in an α- or β-position branched        carbonaceous group;    -   R¹⁰ shall be a C₁-C₁₀ carbonaceous group;    -   R⁴, R⁶, R⁷, R⁸, R¹¹, R¹³, R¹⁴, and R¹⁵ shall each be equal to        hydrogen;    -   R⁵ and R¹² shall each be identical or different and shall be a        C₁-C₂₀ carbonaceous group, where, preferably one or both contain        a cyclic group such as those enumerated above; and    -   R⁹ shall form a bridge between the ligands, which can be shown        by the following formulas:

whereby:

-   -   M² is silicon; and    -   R¹⁶ and R¹⁷ are each identical or different and are each        hydrogen or    -   a C₁-C₂₀ carbonaceous group or a halogen atom.

In another embodiment of the invention, for Formula I:

-   -   M¹ shall be zirconium;    -   R¹ and R² shall be equal and stand for chlorine, methyl or        phenolate;    -   R³ shall be an isopropyl-, isobutyl-, cyclopentyl-, cyclohexyl-,        tert-butyl-, or a phenyl group;    -   R¹⁰ shall be a C₁-C₁₀ carbonaceous alkyl group, preferably a        C₁-C₆ carbonaceous alkyl group; and    -   R⁴, R⁶, R⁷, R⁸, R¹¹, R¹³, R¹⁴, and R¹⁵ shall each be hydrogen;    -   R⁵ and R¹² shall be identical and include a phenyl group which        supports a C₁-C₄ alkyl group, preferably in the para-position;        and    -   R⁹ shall form a bridge between the ligands, which can be shown        by the following formulas:

whereby:

-   -   M² is silicon; and    -   R¹⁶ and R¹⁷ are each identical or different and are hydrogen or        a C₁-C₂₀ carbonaceous group or a halogen atom.

In a more preferred embodiment of the invention, Formula I represents abridged metallocene catalyst, whereby:

-   -   M¹ is zirconium;    -   R¹ and R² are identical and each is chlorine;    -   R³ and R¹⁰ are identical or different and are selected from a        methyl, ethyl, or isopropyl group;    -   R⁴, R⁶, R⁷, R⁸, R¹¹, R¹³, R¹⁴, and R¹⁵ are each a hydrogen;    -   R⁵ and R¹² are identical and are selected from a hydrogen or a        p-t-butylphenyl group; and    -   R⁹ shall form a bridge between the ligands, which can be shown        by the following formula:

whereby:

-   -   M² is silicon; and    -   R¹⁶ and R¹⁷ are each identical and are a methyl group.

Illustrative but non-limiting examples for compounds of Formula I are:

-   Dimethylsilandiyl-bis(2-methyl-indenyl)zirconium dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-isopropyl-phenyl)indenyl)(2-methyl-4-(p-isopropyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tert.-butyl-phenyl)indenyl)(2-methyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tert.-butyl-phenyl)indenyl)(2,7-dimethyl-4-(p-tert.-butyl-phenyl)    indenyl)-zirconium dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tert.-butyl-phenyl)indenyl)(2,5,6,7-tetramethyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-6-methyl-4-(p-tert.-butyl-phenyl)indenyl)(2,6-dimethyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-sec.-butyl-phenyl)indenyl)(2-methyl-4-(p-sec.butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-cyclohexyl-phenyl)indenyl)(2-methyl-4-(p-cyclohexyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-trimethylsilyl-phenyl)indenyl)(2-methyl-4-(p-trimethylsilyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-adamantyl-phenyl)indenyl)(2-methyl-4-(p-adamantyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)(2-methyl-4-(p-tris(trifluoromethyl)methyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-phenyl-indenyl)(2-methyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tert.-butyl-phenyl)indenyl)(2-methyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tert-butyl-phenyl)indenyl)(2,7-dimethyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tert.-butyl-phenyl)indenyl)    (2,5,6,7-tetramethyl-4-phenyl-indenyl)-zirconium dichloride,-   Dimethylsilandiyl-(2-isopropyl-6-methyl-4-(p-tert.-butyl-phenyl)indenyl)(2,6-dimethyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-phenyl-indenyl)(2,7-dimethyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-phenyl-indenyl)(2,5,6,7-tetramethyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-6-methyl-4-phenyl-indenyl)(2,6-dimethyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(p-tert.-butyl-phenyl)indenyl)(2-methyl-4-(4-naphthyl)-indenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-isopropyl-4-(4-naphthyl)-indenyl)indenyl)(2-methyl-4-(p-tert.-butyl-phenyl)indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-[4,5]-benzo-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-indenyl)zirconium dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(1-naphthyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(2-naphthyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-phenyl-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-tert.-butyl-indenyl) zirconium    dichloride, Dimethylsilandiyl-bis(2-isopropyl-4-isopropyl-indenyl)    zirconium dichloride,    Dimethylsilandiyl-bis(2-isopropyl-4-ethyl-indenyl) zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-acenaphth-indenyl) zirconium    dichloride,-   Dimethylsilandiyl-bis(2,4-diisopropyl-indenyl) zirconium dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-methyl-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2,4,6-triisopropyl-indenyl) zirconium    dichloride,-   Dimethylsilandiyl-bis(2,4,5-triisopropyl-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-5-isobutyl-indenyl) zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-5-t-butyl-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-ethyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-trifluoromethyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-methoxy-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert-butyl-phenyl)-indenyl)zirconium    dimethyl,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)zirconium    dimethyl,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-ethyl-phenyl)-indenyl)    zirconium dimethyl,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-trifluoromethyl-phenyl)indenyl)    zirconium dimethyl,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-methoxy-phenyl)-indenyl)    zirconium dimethyl,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)hafnium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)titanium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-n-propyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-n-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-hexyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-ethyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-n-propyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-n-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-hexyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-pentyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-phenyl-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-ethyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-iso-propyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-n-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-hexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-sec-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-propyl-4-(4′-tert.-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-phenyl-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-ethyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-n-propyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-iso-propyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-n-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-hexyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-cyclohexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-sec-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-n-butyl-4-(4′-tert.-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-phenyl-indenyl) zirconium    dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-ethyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-n-propyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-iso-propyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-n-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-n-hexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-cyclohexyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-sec-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-hexyl-4-(4′-tert.-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-phenyl-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-ethyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-n-propyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-iso-propyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-n-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-n-hexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-cyclohexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-sec-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-phenyl-4-(4′-tert.-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconiumbis(dimethylamine),-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconium    dibenzyl,-   Dimethylsilandiyl-bis(2-ethyl-4-(4′-tert.-butyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)    zirconium dimethyl,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-5-azapentalene)(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-6-azapentalene)(2-isopropyl-4-(4′-methyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-ethyl-phenyl)indenyl)zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4-(4′-n-propyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-isopropyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-azapentalene)(2-isopropyl-4-(4′-isopropyl-phenyl)-indenyl)zirconium    dichloride,-   Dimethylsilandiyl-(2,5-dimethyl-6-thiapentalene)(2-isopropyl-4-(4′-isopropyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-oxapentalene)(2-isopropyl-4-(4′-isopropyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-6-azapentalene)(2-isopropyl-4-(4′-n-butyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-5-thiapentalene)(2-isopropyl-4-(4′-n-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-oxapentalene)(2-isopropyl-4-(4′-n-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4-(4′-s-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-oxapentalene)(2-isopropyl-4-(4′-s-butyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-azapentalene)(2-isopropyl-4-(4′-tert.-butyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-n-pentyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-6-azapentalene)(2-isopropyl-4-(4′-n-pentyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-oxapentalene)(2-isopropyl-4-(4′-n-pentyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-n-hexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4-(4′-n-hexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-6-thiapentalene)(2-isopropyl-4-(4′-n-hexyl-phenyl)-indenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2,5-Dimethyl-4-thiapentalene)(2-isopropyl-4-(4′-n-hexyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2,5-Dimethyl-6-thiapentalene)(2-isopropyl-4-(4′-n-hexyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2,5-dimethyl-6-thiapentalene)(2-isopropyl-4-(4′-cyclohexyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-5-thiapentalene)(2-isopropyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-thiapentalene)(2-isopropyl-4-(4′-trimethylsilyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2,5-Dimethyl-4-azapentalene)(2-isopropyl-4-(4′-adamantyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4-(4′-adamantyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-thiapentalene)(2-isopropyl-4-(4′-adamantyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2,5-dimethyl-4-thiapentalene)(2-isopropyl-4-(4′-adamantyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-(4′-tris(trifluoromethyl)-methyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2,5-Dimethyl-4-azapentalene)(2-isopropyl-4-(4′-tris(trifluoromethyl)methyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4-(4′-tris(trifluoromethyl)methyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-thiapentalene)(2-isopropyl-4-(4′-tris(trifluoromethyl)-methyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-6-azapentalene)(2-isopropyl-4-(4′-tert-butyl-phenyl)-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropylindenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-4-azapentalene)(2-isopropylindenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropylindenyl)zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-5-thiapentalene)(2-isopropylindenyl)zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-thiapentalene)(2-isopropylindenyl)    zirconium dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-5-azapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-azapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-4-azapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-5-azapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-5-thiapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-thiapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-oxapentalene)(2-isopropyl-4-phenyl-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-azapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-4-azapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-5-azapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-N-phenyl-6-azapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-thiapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-5-thiapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-thiapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-4-oxapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-5-oxapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-(2-methyl-6-oxapentalene)(2-isopropyl-4,5-benzo-indenyl)-zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-azapentalene)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-N-phenyl-4-azapentalene)zirconium    dichloride,-   Dimethylsilandiyl-bis(2-isopropyl-4-thiapentalene)zirconium    dichloride,    as well as the corresponding titanium and hafnium compounds and also    various bridges of dimethylsilandiyl according to Formula I such as    dimethylmethandiyl, diphenylmethandiyl, ethandiyl,    1,2-dimethylethandiyl, dipropylsilandiyl, dibutylsilandiyl,    dipentylsilandiyl, dihexylsilandiyl, diheptylsilandiyl,    dioctylsilandiyl, dinonylsilandiyl, didecylsilanediyl,    diundecylsilandiyl, didodecylsilandiyl.

The synthesis of the compounds of Formula I according to the inventioncan be conducted according to processes known to one skilled in the art.An example therefor is set forth in the following schematic.

The compounds of Formula I according to the invention are particularlysuited to be components of catalyst systems to manufacture polyolefinsthrough the polymerization of at least one olefin in the presence of acatalyst that contains at least one compound of Formula I according tothe invention, and optionally at least one co-catalyst.

Ethylene is preferred as the olefin. In a preferred embodiment of theinvention, ethylene is polymerized using the catalysts of the invention,whereby polymerization is understood to be both the homo-polymerizationof ethylenes as well as the co-polymerization of ethylene with otherolefins. The ethylene used in the process can, if desired, contain stillother olefins that are selected from the group that is formed by:1-olefins (or alpha-olefins) with 3-20, preferably 3 to 10 C atoms, suchas propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, or4-methyl-1-pentene; dienes such as 1,3-butadiene or 1,4-hexadiene; andcyclo-olefins such as styrene, norbornene, methyl norbornene, vinylnorbornene, cyclopentadiene, norbornadiene, ethyl norbornadiene ortetracyclododecene; as well as mixtures of same.

Particular preference is given to co-polymerizing the ethylene used withone or more olefins with 3 to 8 C atoms such as propene, 1-butene,1-pentene, 1-hexene, styrene or butadiene.

A co-monomer fraction of 0.1 to 10% is suitable, preferably 0.5 to 9%and in particular 2 to 5%. Particular preference is given to theco-polymerization of ethylene with the co-monomer propene.

Further preference is given to the process according to the inventionwhereby the ethylene used is homo-polymerized, or co-polymerized withpropene.

Particular preference is given to the process according to the inventionwhereby the ethylene used is homo-polymerized.

The ethylene polymers and co-polymers manufactured with the processaccording to the invention are high to ultra high molecular weight,since they have a viscosimetrically determined molecular weight of atleast about 0.7×10⁶ g/mol and preferably greater than 1×10⁶ g/mol.Preference is given to polyethylenes with a molecular weight of greaterthan 1×10⁶ g/mol that can be obtained using the process according to theinvention.

The viscosimetric measurements are made in DECALIN® at 135° C. and aconcentration of 0.1 g (polymer)/1 L (DECALIN®). The molecular weightcan be derived from the viscosity number.

The polymerization is conducted at a temperature of −20 to 300° C.,preferably 0 to 200° C., most especially preferred at 20 to 100° C. Thepressure is from 0.5 to 2000 bar, preferably 1 to 64 bar. Thepolymerization can be conducted in solution, in bulk, in suspension orin emulsion, continuously or in batches, in one or more stages. Suitablesolvents for the polymerization are, for example, aliphatic hydrocarbonssuch as pentane, hexane and the like or aromatic hydrocarbons such asbenzene, toluene, xylene and the like, or ethers such as diethyl ether,dibutyl ether, methyl-tert-butyl ether, tetrahydrofuran, dioxane,anisole, diphenyl ether and ethyl-phenyl ether, as well as halogenatedsolvents such as dichloromethane, trichloromethane, chloro-benzene,bromo-benzene and the like. Mixtures of various solvents in variousproportions can also be used according to the invention.

Ultra high molecular weight ethylene polymers and co-polymers areobtained through the polymerization of at least one olefin in thepresence of catalyst systems of at least one compound of Formula I andone co-catalyst.

In a preferred embodiment of the invention, the catalyst system used inthe process according to the invention contains at least oneco-catalyst.

The co-catalyst that, together with at least one transition metalcompound of Formula I, forms the catalyst system, contains at least onealuminoxane compound, or another Lewis acid, or an ionic compound, whichreacts with the transition metal compound to convert it into a cationiccompound.

Particular preference is given to catalyst systems that contain at leastone Lewis acid as co-catalyst.

As aluminoxane, preference is given to using a compound of the generalFormula II.

(R AlO)q  Formula II

Other suitable aluminoxanes may be cyclic, and can have the structureshown, for example, in Formula III

or may be linear as in Formula IV

or may be of a cluster type as in Formula V.

Such aluminoxanes are, for example, described in JACS 117 (1995),6465-74, Organometallics 13 (1994), 2957-2969.

The radical R in the Formulas II, III, IV and V may be identical ordifferent and are each a C₁-C₂₀-hydrocarbon group such as a C₁-C₆ alkylgroup, a C₆-C₁₈ aryl group, benzyl or hydrogen, and q stands for aninteger of 2 to 50, preferably 10 to 35. Preferably, the radicals R areidentical and are each methyl, isobutyl, n-butyl, phenyl or benzyl, inparticular methyl.

If the radicals R are different, they are preferably methyl andhydrogen, methyl and isobutyl, or methyl and n-butyl, containinghydrogen or isobutyl or n-butyl preferably up to 0.01-40% (number ofradicals R).

The aluminoxane can be manufactured in various ways according to knownprocesses. One of the methods is, for example, reacting an aluminumhydrocarbon compound and/or a hydridoaluminum hydrocarbon compound withwater (gaseous, solid, liquid or bound—for example as water ofcrystallization) in an inert solvent (such as toluene).

To prepare an aluminoxane having different alkyl groups R, two differentaluminum trialkyls (AIR₃+AIR′₃), corresponding to the desiredcomposition and reactivity, are reacted with water (see S. Pasynkiewicz,Polyhedron 9 (1990) 429 and EP-A-0,302,424).

Regardless of the type of preparation, a variable content of unreactedaluminum feed compound, present in free form or as an adduct, is commonto all aluminoxane solutions.

As Lewis acid, preference is given to using at least one boron ororganoaluminum compound containing C₁-C₂₀ carbonaceous groups, includingbranched or unbranched alkyl or haloalkyl groups, such as methyl,propyl, isopropyl, isobutyl, trifluoromethyl, and unsaturated groupsincluding aryls or haloaryls, such as phenyl, tolyl, benzene groups,p-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl,pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5di(trifluoromethyl)phenyl.

Examples of Lewis acids are trimethylaluminum, triethylaluminum,triisobutylaluminum, tributylaluminum, trifluoroborane, triphenylborane,tris(4-fluorophenyl)borane, tris(3,5-difluorophenyl)borane,tris(4-fluoromethylphenyl)borane, tris(pentafluorophenyl)borane,tris(tolyl)borane, tris(3,5-dimethylphenyl)borane,tris(3,5-difluorophenyl)borane, and/ortris(3,4,5-trifluorophenyl)borane. Particular preference is given totris(pentafluorophenyl)borane.

As ionic cocatalysts, preference is given to using compounds thatcontain a noncoordinating anion, such astetrakis(pentafluorophenyl)-borate, tetraphenylborate, SbF₆—, CF₃SO₃— orClO₄—.

As cationic counterions, use is made of protonated Lewis bases such as,for example, methyl amine, aniline, N,N-dimethylbenzylamine, as well astheir derivatives, N,N-dimethylcyclohexylamine and its derivatives,dimethylamine, diethylamine, N-methylaniline, diphenylamine,N,N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine,methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline,p-nitro-N,N-dimethylaniline, triethylphosphine, triphenylphosphine,diphenylphosphine, tetrahydrothiophene, or triphenylcarbenium.

Examples of such ionic compounds are:

-   Triethylammoniumtetra(phenyl)borate,-   Tributylammoniumtetra(phenyl)borate,-   Trimethylammoniumtetra(tolyl)borate,-   Tributylammoniumtetra(tolyl)borate,-   Tributylammoniumtetra(pentafluorophenyl)borate,-   Tributylammoniumtetra(pentafluorophenyl)aluminate,-   Tripropylammoniumtetra(dimethylphenyl)borate,-   Tributylammoniumtetra(trifluoromethylphenyl)borate,-   Tributylammoniumtetra(4-fluorophenyl)borate,-   N,N-Dimethylaniliniumtetra(phenyl)borate,-   N,N-Diethylaniliniumtetra(phenyl)borate,-   N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)borate,-   N,N-Dimethylaniliniumtetrakis(pentafluorophenyl)aluminate,-   Di(propyl)ammoniumtetrakis(pentafluorophenyl)borate,-   Di(cyclohexyl)ammoniumtetrakis(pentafluorophenyl)borate,-   Triphenylphosphoniumtetrakis(phenyl)borate,-   Triethylphosphoniumtetrakis(phenyl)borate,-   N,N-Dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate,-   N,N-Dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate,-   Diphenylphosphoniumtetrakis(phenyl)borate,-   Tri(methylphenyl)phosphoniumtetrakis(phenyl)borate,-   Tri(dimethylphenyl)phosphoniumtetrakis(phenyl)borate,-   Triphenylcarbeniumtetrakis(pentafluorophenyl)borate,-   Triphenylcarbeniumtetrakis(pentafluorophenyl)aluminate,-   Triphenylcarbeniumtetrakis(phenyl)aluminate,-   Ferroceniumtetrakis(pentafluorophenyl)borate and/or-   Ferroceniumtetrakis(pentafluorophenyl)aluminate.

Preference is given totriphenylcarbeniumtetrakis(pentafluorophenyl)borate and/orN,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.

Mixtures of at least one Lewis acid and at least one ionic compound canalso be used.

Further suitable cocatalyst components are borane or carborane compoundssuch as:

-   7,8-dicarbaundecaborane(13),-   Undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,-   Dodecahydride-1-phenyl-1,3-di-carbanonaborane,-   Tri(butyl)ammoniumundecahydride-8-ethyl-7,9-dicarbaundecaborate,-   4-carbanonaborane(14)bis(tri(butyl)ammonium)nonaborate,-   Bis(tri(butyl)ammonium)undecaborate,-   Bis(tri(butyl)ammonium)dodecaborate,-   Bis(tri(butyl)ammonium)decachlorodecaborate,-   Tri(butyl)ammonium-1-carbadecaborate,-   Tri(butyl)ammonium-1-carbadodecaborate,-   Tri(butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,-   Tri(butyl)ammoniumbis(nonahydride-1,3-di-carbonnonaborate)cobaltate(III),    and-   Tri(butyl)ammoniumbis(undecahydride-7,8-carbaundecaborate)ferrate(III).

Further useful co-catalyst systems are combinations of at least one ofthe aforementioned amines and if desired, a support with organo-elementcompounds, as they are described in WIPO Publication No. WO 99/40129(and equivalent U.S. Pat. No. 6,482,902), the entireties of which areincorporated herein by reference.

The supports with organoelement compounds named in WO99/40129 are alsocomponents of this invention.

Preferred components of these co-catalyst systems are the compounds ofFormulas A and B,

whereby:

-   -   R¹⁸ is a hydrogen atom, a halogen atom, a C₁-C₂₀ carbonaceous        group, in particular C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, C₁-C₁₀        alkoxy, C₆-C₂₀ aryl, C₆-C₂₀ haloaryl, C₆-C₂₀ aryloxy, C₇-C₂₀        arylalkyl, C₇-C₄₀ haloarylalkyl, C₇-C₂₀ alkylaryl or C₇-C₂₀        haloalkylaryl. R¹⁸ can also be an OSiR₃ group, whereby R is        identical or different and has the same meaning as the        definition of R¹⁸ provided immediately above.

Further preferred co-catalysts are general compounds that are formed bythe reaction of at least one compound of Formula C and/or D and/or Ewith at least one compound of formula F.

whereby:

-   -   R¹⁸ has the same meaning as mentioned above; and    -   R¹⁹ can be a hydrogen atom or a boron free C₁-C₂₀ carbonaceous        group such as C₁-C₂₀ alkyl, C₆-C₂₀ aryl, C₇-C₂₀ arylalkyl,        C₇-C₂₀ alkylaryl; and    -   X¹ is an element of the 16^(th) group of the periodic table or        an NR group, whereby R is a hydrogen atom or a C₁-C₂₀        hydrocarbon radical such as C₁-C₂₀-Alkyl or C₁-C₂₀ Aryl; and    -   L is an element of the 16^(th) group of the periodic table or an        NR group, whereby R is a hydrogen atom or a C₁-C₂₀ hydrocarbon        radical such as C₁-C₂₀-alkyl or C₁-C₂₀ aryl;    -   f is an integer from 0 to 3; and    -   g is an integer from 0 to 3.

If desired, the organoelement compounds are combined with anorganometallic compound of Formulas II to V and/or VI,

[M³R²⁰ _(r)]_(k)  Formula VI

whereby:

-   -   M³ is an element of the 1^(st), 2^(nd), or 13^(th) group of the        periodic table; R²⁰ is identical or different and is a hydrogen        atom, a halogen atom, a C₁-C₄₀ carbonaceous group, in particular        a C₁-C₂₀ alkyl, a C₆-C₂₀ aryl, a C₇-C₂₀ aryl-alkyl, or a C₇-C₂₀        alkyl-aryl group; r is an integer from 1 to 3; and k is an        integer of 1 to 4.

Examples for the co-catalytically effective compounds of Formulas A andB are:

The organometallic compounds of Formula F are preferably uncharged Lewisacids. Examples of preferred organometallic compounds of Formula F aretrimethylaluminum, triethylaluminum, triisopropylaluminum,trihexylaluminum, trioctylaluminum, tri-n-butylaluminum,tri-n-propylaluminum, triisoprenealuminum, dimethylaluminummonochloride, diethylaluminum monochloride, diisobutylaluminummonochloride, methylaluminum sesquichloride, ethylaluminumsesquichloride, dimethylaluminum hydride, diethylaluminum hydride,diisopropylaluminum hydride, dimethylaluminum-(trimethylsiloxide),dimethylaluminum(triethylsiloxide), phenylalane, pentafluorophenylalane,and o-tolylalane.

Further co-catalysts, which may be in unsupported or supported form, arethe compounds mentioned in EP-A-924223 (equivalent of U.S. Pat. No.6,444,603), EP-A-601830 (equivalent of U.S. Pat. No. 5,449,650),EP-A-824112 (equivalent of U.S. Pat. No. 6,329,313), EP-A-824113(equivalent of U.S. Pat. No. 6,124,231), EP-A-811627 (equivalent ofDE-A-19622207 and U.S. Pat. No. 6,255,531), WO 97/11775 (equivalent ofU.S. Pat. No. 6,271,164), and DE-A-19606167 (equivalent of U.S. Pat. No.6,350,829), the entireties of which are incorporated herein byreference.

Moreover, the catalysts according to the invention can be homogeneouslyas well as heterogeneously supported.

In a preferred embodiment, the compound of Formula I used in the processaccording to the invention is used in a supported form.

The support component of the catalyst system can be any organic orinorganic inert solid, in particular a porous support such as talc,inorganic oxides and finely divided polymer powder (e.g., polyolefin).

Suitable inorganic oxides may be found in the groups 2, 3, 4, 5, 13,14,15, and 16 of the periodic table. Examples for the oxides preferredas supports include silicon dioxide, aluminum oxide, and also mixedoxides of the elements calcium, aluminum, silicon, magnesium, titaniumand corresponding oxide mixtures as well as hydrotalcite. Otherinorganic oxides that can be used either alone or in combination withthe aforementioned preferred oxidic supports, are, e.g., MgO, ZrO₂, TiO₂or B₂O₃, to name a few.

The support materials used have a specific surface area in the rangefrom 10 to 1000 m²/g, a pore volume in the range from 0.1 to 5 ml/g anda mean particle size of 1 to 500 μm. Preference is given to supportswith a specific surface area in the range of 50 to 500 m² μg, a porevolume in the range from 0.5 to 3.5 ml/g and a mean particle size in therange of 5 to 350 μm. Particular preference is given to supports havinga specific surface area in the range from 200 to 400 m²/g, a pore volumein the range from 0.8 to 3.0 ml/g, and a mean particle size of 10 to 200μm.

If the support material naturally exhibits a low moisture content orresidual solvent content, the dehydration or drying before use can beomitted. If this is not the case, as when using silica gel as supportmaterial, dehydration or drying is advisable. Thermal dehydration ordrying of the support material can be carried out under a vacuum and asimultaneous blanketing with inert gas (e.g., nitrogen). The dryingtemperature is in the range from 100 to 1000° C., preferably from 200 to800° C. The pressure is not critical in this instance. The dryingprocess can last from 1 to 24 hours. Shorter or longer drying times arepossible, provided that establishment of equilibrium with the hydroxylgroups on the support surface can take place under the conditionschosen, which normally takes from 4 to 8 hours.

Dehydration or drying of the support material can also be carried out bychemical means, by reacting the adsorbed water and the hydroxyl groupson the surface with suitable passivating agents. Reaction with thepassivating reagent can convert all or part of the hydroxyl groups intoa form which does not lead to any adverse interaction with thecatalytically active centers. Suitable passivating agents are, forexample, silicon halides and silanes, e.g. silicon tetrachloride,chlortrimethylsilane, dimethylamino trichlorosilane, or organometalliccompounds of aluminum, boron and magnesium, for exampletrimethylaluminum, triethylaluminum, triisobutylaluminum,triethylborane, or dibutylmagnesium. Chemical dehydration or passivationof the support material is carried out, for example, by reacting asuspension of the support material in a suitable solvent with thepassivating reagent either in pure form or as a solution in a suitablesolvent in the absence of air and moisture. Suitable solvents are, forexample, aliphatic or aromatic hydrocarbons such as pentane, hexane,heptane, toluene or xylene. Passivation is carried out at from 25° C. to120° C., preferably from 50° C. to 70° C. Higher and lower temperaturesare possible. The reaction time is from 30 minutes to 20 hours,preferably from 1 to 5 hours. After the chemical dehydration iscomplete, the support material is isolated by filtration under inertconditions, washed one or more times with suitable inert solvents asdescribed above and subsequently dried in a stream of inert gas or underreduced pressure.

Organic support materials such as finely divided polyolefin powders(e.g., polyethylene, polypropylene or polystyrene) can also be used andshould likewise be freed of adhering moisture, solvent radicals or otherimpurities by appropriate purification and drying operations prior touse.

To prepare the supported catalyst system, at least one of theabove-described compounds of Formula I is brought in contact with atleast one co-catalyst component in a suitable solvent, preferably givinga soluble reaction product, an adduct or a mixture.

The preparation so obtained is then mixed with the dehydrated orpassivated support material, the solvent removed and the resultingsupported catalyst system dried, to ensure that all or most of thesolvent is removed from the pores of the support materials. Thesupported catalyst is obtained as a free flowing powder.

Another object of the present invention is a process to provide a freeflowing and, if desired, pre-polymerized supported catalyst systemcomprising the following steps:

-   -   a) preparation of a mixture of at least one compound of Formula        I and at least one co-catalyst in a suitable solvent or        suspension medium;    -   b) application of the mixture obtained from Step a) to a porous,        preferably inorganic, dehydrated support;    -   c) removal of most of the solvent from the resulting mixture;    -   d) isolation of the supported catalyst system; and    -   e) if desired, a pre-polymerization of the supported catalyst        system obtained using one or several olefinic monomer(s), to        obtain a pre-polymerized supported catalyst system.

Preferred solvents in step a) are hydrocarbons and hydrocarbon mixturesthat are liquid at the reaction temperature chosen and in which theindividual components are preferably dissolved. The solubility of theindividual components is, however, not a prerequisite, as long as thereaction product from the compound of Formula I and the co-catalyst issoluble in the solvent chosen. Examples for the suitable solventsinclude alkanes such as pentane, isopentane, hexane, heptane, octane,and nonane; cycloalkanes such as cyclopentane and cyclohexane; andaromatics such as benzene, toluene, ethylbenzene and diethylbenzene.Very particular preference is given to toluene.

The amounts of aluminoxane and compound of Formula I used in thepreparation of the supported catalyst system can be varied over a widerange. Preference is given to a molar ratio of aluminum to transitionmetal in the compound of Formula I of 10:1 to 1000:1, very particularlypreferably from 50:1 to 500:1.

In the case of methylaluminoxane preference is given to using 30%strength toluene solutions; the use of 10% strength solutions is,however, also possible. To carry out the preactivation, the compound ofFormula I in the form of a solid is dissolved in a solution of thealuminoxane in a suitable solvent. It is also possible to dissolve thecompound of Formula I separately in a suitable solvent and then tocombine this solution with the aluminoxane solution. Preference is givento using toluene.

The preactivation time is from 1 minute to 200 hours.

The preactivation can take place at room temperature (25° C.). The useof higher temperatures can, in certain cases, shorten the time requiredfor the preactivation and produce an additional increase in activity. Inthis case, a higher temperature means a range from 50° C. to 10° C.

The pre-activated solution or the mixture is then combined with an inertsupport material, usually silica gel, which is in the form of a drypowder or as a suspension in one of the aforementioned solvents.

Preference is given to using the support material in the form of powder.The order of addition is immaterial. The preactivated metalloceneco-catalyst solution or the metallocene co-catalyst mixture can be addedto the support material or else the support material can be introducedto the catalyst mixture.

The volume of the preactivated solution or the metallocene co-catalystmixture can exceed 100% of the total pore volume of the support materialused or else can be up to 100% of the total pore volume.

The temperature at which the preactivated solution or the metalloceneco-catalyst mixture is brought in contact with the support material canvary in the range from 0° C. to 100° C. Lower or higher temperaturesare, however, also possible.

All or the major part of the solvent is subsequently removed from thesupported catalyst system, whereby the mixture can be stirred and, ifnecessary, also heated. Preference is given to removing both the visibleportion of the solvent as well as the portion in the pores of thesupport material. The removal of the solvent can be carried out in aconventional fashion with application of vacuum and/or flushing withinert gas. In the drying process, the mixture can be heated until thefree solvent has been removed, which usually takes from 1 to 3 hours ata preferred temperature of from 30° C. to 60° C. The free solvent is thevisible portion of solvent in the mixture. In this context, residualsolvent is the portion which is enclosed in the pores. As an alternativeto complete removal of the solvent, it is also possible for thesupported catalyst system to be dried only to a particular residualsolvent content, with the free solvent having been completely removed.The supported catalyst system can subsequently be washed with alow-boiling hydrocarbon such as pentane or hexane and dried again.

The supported catalyst system can either be used directly for thepolymerization of olefins or can be prepolymerized using one or moreolefinic monomers prior to use in a polymerization process. An exampleof the prepolymerization of supported catalyst systems is described inWO 94/28034.

A small amount of an olefin, preferably an α-olefin (for example vinylcyclohexane, styrene or phenyldimethylvinylsilane) as modifyingcomponent or an anti-static (as described in U.S. patent applicationSer. No. 08/365,280) can be added as additive during or after thepreparation of the supported catalyst system. The molar ratio ofadditive to metallocene components (compound according to Formula I) ispreferably from 1:1000 to 1000:1, very particularly preferably from 1:20to 20:1.

Another object of the invention is the use of the catalyst systemsaccording to the invention, containing at least one compound accordingto Formula I and at least one co-catalyst to manufacture high to ultrahigh molecular weight ethylene homo- or co-polymers.

Particular preference is given to the catalyst system being present in asupported form.

The invention is depicted through the following examples, which are notintended to limit the invention, the scope of which is set forth in theappended claims.

EXAMPLES

General information: preparation and handling of organometalliccompounds were carried out in the absence of air and moisture underargon (using the Schlenk technique or a glove box). All solventsrequired were purged with argon and dried over molecular sieves beforeuse.

The following catalysts are used in the examples:

Example 1 Production of the Supported Catalysts 1. Activation:

In an annealed flask under inert gas 0.128 mmol catalyst is dissolved in20 ml toluene and mixed with 6 ml (28.8 mmol, 1.672 g) methylaluminoxane(MAO; 30% in toluene). The mixture is stirred for one hour at roomtemperature.

2. Support:

In an annealed flask under inert gas 6 g SiO₂ (Grace XPO 2107, dried) isplaced and suspended with 30 ml abs. toluene. A suspension results thatcan be slightly stirred, to which the activated catalyst (from 1) isthen added. It is stirred for 10 min and then the solvent is removed ina vacuum to up to no more than 5% residual moisture.

Examples 2-6 Homopolymerization of Ethylene

In a 2 L steel autoclave 1.5 L EXXSOL® is placed and mixed with 15 mmolof an aluminum alkyl (e.g., tri-isobutylaluminum). The reactor is thenbrought to the desired temperature and an ethylene pressure of 7-15 baris built up. At the start of the polymerization 9 μmol of the relevantcatalyst (see Table 1) suspended in EXXSOL® is added. It is polymerizedfor one hour and the reaction is stopped when the ethylene pressuredegrades. The polymer is filtered and dried in a vacuum at 80° C.Finally, the yield and the molecular weight are determined.

TABLE 1 Pressure Example Catalyst C2 Temperature Yield M_(v) 2 1 10 bar70° C. 70 g 0.7 × 10⁶ g/mol 3 2 10 bar 70° C. 61 g 2.2 × 10⁶ g/mol 4 310 bar 70° C. 64 g 1.1 × 10⁶ g/mol 5 4 10 bar 70° C. 98 g 1.8 × 10⁶g/mol 6 5 10 bar 70° C. 114 g  2.7 × 10⁶ g/mol

The above table therefore shows that heterogeneous polymerizationaccording to the inventive process using the bridged metallocenecatalysts of the invention achieves high to ultra high molecular weightpolyethylene products. Note that ultra high molecular weight productsare formed only when the bridged metallocene catalysts of the inventionhaving substituent carbonaceous groups with more than one carbon,particularly at the R³ position, are used. Additionally, in severalembodiments, higher substitution of the inventive catalyst at the R³position in combination with higher substitution at the R⁵ and R¹²positions provide for significantly improved yields.

While the invention has been illustrated in connection with severalexamples, modifications to these examples within the spirit and scope ofthe invention will be readily apparent to those of skill in the art. Inview of the foregoing discussion, relevant knowledge in the art andreferences discussed above, the disclosures of which are allincorporated herein by reference, further description is deemedunnecessary.

1. A process of manufacturing high, very high, and ultra high molecularweight polymers comprising predominantly ethylene monomers, wherein theprocess comprises reacting ethylene monomers, and optionally additionalolefin monomers, in the presence of a catalyst system which includes acatalytic compound of Formula I to produce a polymer having aviscosimetrically-determined molecular weight of 0.7×10⁶ g/mol orgreater

whereby: M¹ is a transition metal of the 4^(th) to 6^(th) group of theperiodic table, wherein the oxidation level of said transition metaldoes not equal zero; R¹ is hydrogen or a C₁-C₂₀-carbonaceous group or ahalogen atom; R² is hydrogen or a C₁-C₂₀ carbonaceous group or a halogenatom; R³ and R¹⁰ are each identical or different and are each a C₁-C₂₀carbonaceous group; R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, and R¹⁵ areeach identical or different and are each hydrogen or a halogen atom or aC₁-C₂₀ carbonaceous group, whereby, optionally, two or severalconsecutively form a cyclic system; and R⁹ is a bridge between theligands, which is represented by one of the following formulas:

whereby: M² is either silicon, germanium or tin; and R¹⁶ and R¹⁷ areeach identical or different and are each hydrogen or a C₁-C₂₀carbonaceous group or a halogen atom.
 2. The process according to claim1, wherein M¹ is selected from the group consisting of Ti, Zr, Hf, V,Mo, Cr and Nb.
 3. The process according to claim 1, wherein at least oneof R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, and R¹⁵ includes a cyclicgroup.
 4. The process according to claim 1, wherein for the compound ofFormula I: M¹ is a transition metal of the 4^(th) group of the periodictable, wherein the oxidation level of said transition metal does notequal zero; R¹ is hydrogen, a C₁-C₂₀-carbonaceous group, or a halogenatom; R² is hydrogen, a C₁-C₂₀ carbonaceous group, or a halogen atom; R³is a C₁-C₂₀ carbonaceous group; R¹⁰ is a C₁-C₁₀ carbonaceous group; R⁴,R⁶, R⁷, R⁸, R¹¹, R¹³, R¹⁴, and R¹⁵ are each hydrogen; R⁵ and R¹² areeach identical or different and are a C₁-C₂₀ carbonaceous group, ofwhich at least one includes a cyclic group; and R⁹ is a bridge betweenthe ligands, which is represented by one of the following formulas:

whereby: M² is silicon; and R¹⁶ and R¹⁷ are each identical or differentand are each hydrogen or a C₁-C₂₀ carbonaceous group or a halogen atom.5. The process according to claim 4, wherein R⁵ and R¹² are identical ordifferent and are selected from the group consisting of C₆-C₂₀ aryl,C₆-C₂₀ fluoroaryl, C₆-C₂₀ aryloxy, C₇-C₂₀ arylalkyl, C₇-C₂₀ alkylaryl,C₇-C₂₀ aryloxyalkyl, C₁₂-C₂₀ aryloxyaryl, C₅-C₂₀ heteroaryl, C₄-C₂₀heterocycloalkyl, C₈-C₂₀ arylalkenyl, and C₈-C₂₀ arylalkinyl.
 6. Theprocess according to claim 4, wherein both of R⁵ and R¹² include acyclic group.
 7. The process according to claim 4, wherein R³ is an α-or β-position branched carbonaceous group or a carbonaceous groupcyclized in a α- or β-position.
 8. The process according to claim 1,wherein for the compound of Formula I: M¹ is zirconium; R¹ and R² areidentical and are each chlorine, methyl or phenolate; R³ is anisopropyl-, isobutyl-, cyclopentyl-, cyclohexyl-, tert-butyl-, or aphenyl group; R¹⁰ is a C₁-C₁₀ carbonaceous group and is an alkyl group;R⁴, R⁶, R⁷, R⁸, R¹¹, R¹³, R¹⁴, and R¹⁵ are each hydrogen; R⁵ and R¹² areidentical or different and are each a C₁-C₂₀ carbonaceous group, whereinat least one includes a phenyl group which supports a C₁-C₄ alkyl group;and R⁹ is a bridge between the ligands, which is represented by one ofthe following formulas:

whereby: M² is silicon; and R¹⁶ and R¹⁷ are each identical or differentand are hydrogen or a C₁-C₂₀ carbonaceous group or a halogen atom. 9.The process according to claim 8, wherein R⁵ and R¹² are identical andinclude a phenyl group which supports a C₁-C₄-alkyl group in the paraposition.
 10. The process according to claim 1, wherein for the compoundof Formula I: M¹ is zirconium; R¹ and R² are identical and each ischlorine; R³ and R¹⁰ are identical or different and are selected from amethyl, ethyl, or isopropyl group; R⁴, R⁶, R⁷, R⁸, R¹¹, R¹³, R¹⁴, andR¹⁵ are each a hydrogen; R⁵ and R¹² are identical and are selected froma hydrogen or a p-t-butylphenyl group; and R⁹ is a bridge between theligands, which is represented by the following formula:

whereby: M² is silicon; and R¹⁶ and R¹⁷ are each identical and are amethyl group.
 11. The process according to claim 1, wherein the compoundof Formula I has a structure corresponding to one or more of thefollowing:


12. The process according to claim 1, wherein the compound of Formula Ihas a structure corresponding to the following:


13. The process according to claim 1, wherein the compound of Formula Ihas a structure corresponding to the following:


14. The process according to claim 1, wherein the compound of Formula Ihas a structure corresponding to the following:


15. The process according to claim 1, wherein the compound of Formula Ihas a structure corresponding to the following:


16. The process according to claim 1, wherein the compound of Formula Ihas a structure corresponding to the following:


17. The process according to claim 1, wherein ethylene is reacted in thepresence of the catalyst system to produce a polyethylene homopolymer.18. The process according to claim 1, wherein ethylene is reacted withadditional olefin monomers in the presence of the catalyst system toproduce a copolymer comprising predominantly ethylene monomers.
 19. Theprocess according to claim 18, wherein the additional olefin monomersare characterized by having 3-20 carbon atoms.
 20. The process accordingto claim 18, wherein the additional olefin monomers are characterized byhaving 3-10 carbon atoms.
 21. The process according to claim 18, whereinthe additional olefin monomers are selected from the group consisting ofpropene, butene, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-pentene,1-octene, styrene, 1,3-butadiene, 1,4-hexadiene, vinyl norbornene,norbornadiene, ethyl norbornadiene, norbornene, cyclopentadiene,tetracyclododecene, methylnorbornene, and combinations thereof.
 22. Theprocess according to claim 18, wherein the additional olefin monomersinclude an alpha olefin having 3 to 8 carbon atoms.
 23. The processaccording to claim 21, wherein the olefin is selected from the groupconsisting of propene, butene, 1-pentene, 1-hexene, styrene, butadiene,and combinations thereof.
 24. The process according to claim 18, whereinthe ethylene is co-polymerized with propene.
 25. The process accordingto claim 18, wherein the fraction of additional olefin monomers is 0.1to 10 weight % of the total monomers reacted.
 26. The process accordingto claim 1, wherein the process produces a polymer having aviscosimetrically-determined molecular weight of greater than 1×10⁶g/mol.
 27. The process according to claim 1, wherein the processproduces a polymer having a molecular weight distribution M_(w)/M_(n) offrom 2 to
 6. 28. The process according to claim 1, wherein the catalystsystem contains at least one co-catalyst.
 29. The process according toclaim 28, wherein the co-catalyst is a Lewis acid.
 30. The processaccording to claim 28, wherein the co-catalyst is an aluminoxanecompound.
 31. The process according to claim 28, wherein the co-catalystis a methylaluminoxane compound.
 32. The process according to claim 30,wherein the co-catalyst is present in the catalyst system in a molarratio of aluminum to transition metal of 10:1 to 1000:1.
 33. The processaccording to claim 1, wherein the compound in Formula I is present in asupported form.
 34. A method of using a catalyst system to produce high,very high, and ultra-high molecular weight ethylene homopolymer orcopolymers, wherein the method comprises reacting ethylene in thepresence of said catalyst system to produce a polymer comprisingpredominantly ethylene monomers and having aviscosimetrically-determined molecular weight of at least 0.7×10⁶ g/mol,and wherein said catalyst system comprises: (i) at least one catalysthaving the formula:

whereby: M¹ is a transition metal of the 4^(th) to 6^(th) group of theperiodic table, wherein the oxidation level of said transition metaldoes not equal zero; R¹ is hydrogen or a C₁-C₂₀-carbonaceous group or ahalogen atom; R² is hydrogen or a C₁-C₂₀ carbonaceous group or a halogenatom; R³ and R¹⁰ are each identical or different and are each a C₁-C₂₀carbonaceous group; R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹³, R¹⁴, and R¹⁵ areeach identical or different and are each hydrogen or a halogen atom or aC₁-C₂₀ carbonaceous group, whereby, optionally, two or severalconsecutively form a cyclic system; and R⁹ is a bridge between theligands, which is represented by one of the following formulas:

whereby: M² is either silicon, germanium or tin; and R¹⁶ and R¹⁷ areeach identical or different and are each hydrogen or a C₁-C₂₀carbonaceous group or a halogen atom; and (ii) at least one co-catalyst.35. A process of manufacturing high, very high, and ultra high molecularweight polymers comprising predominantly ethylene monomers, wherein theprocess comprises reacting ethylene in the presence of a catalyst systemto produce a polymer having a viscosimetrically-determined molecularweight of at least 0.7×10⁶ g/mol, wherein the catalyst system comprisesa bridged metallocene catalyst compound having a zirconium dichloridecentral functionality and a dimethyl silandiyl bridge betweenfive-membered rings of the metallocene compound, and wherein the ringsare indenyl groups, with the proviso that both rings are substituted atthe 2-position with respect to the dimethyl silandiyl bridge with aC₁-C₂₀ carbonaceous group.
 36. The process according to claim 35,wherein at least one of the rings is substituted with a C₂-C₂₀carbonaceous group at the 2-position with respect to the dimethylsilandiyl bridge.
 37. The process according to claim 35, wherein thereaction occurs at a temperature of from −20° C. to 300° C.
 38. Theprocess according to claim 35, wherein the reaction occurs at a pressureof from 0.5 bar to 2000 bar.